FR2814945A1 - Treatment of grey hair for cosmetics to restore natural pigmentation to grey hair comprises application of composition of catalytic system comprising salt or oxide of manganese and/or zinc and alkaline and/or alkaline earth hydrocarbonate - Google Patents

Abstract

Treatment of grey hair comprises application of composition comprising, in physiologically acceptable medium, effective amount of catalytic system comprising first component selected from salts and oxides of bivalent manganese and/or zinc, and second component selected from alkaline and alkaline earth hydrocarbonates and their mixtures. Treatment of grey hair comprises application of composition comprising, in physiologically acceptable medium, effective amount of catalytic system comprising first component selected from salts and oxides of bivalent manganese and/or zinc, and second component selected from alkaline and alkaline earth hydrocarbonates and their mixtures. The proportion of first and second components of catalytic system are such that (Mn(II))/(HCO3) is up to 1, when (Mn(II)) is not 0; (Zn(II))/(HCO3) is up to 1 when (Zn(II)) is not 0; and (Mn(II) + (Zn(II))/(HCO3) is up to 1 when neither of (Mn(II)) and (Zn(II)) is 0, with (Mn(II)), (Zn(II)) and (HCO3) representing respectively molar concentrations of Mn(II), Zn(II) and (HCO3) in the composition.

Description

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. The present invention relates generally to a method of treating canities.

 The appearance of white hair in humans is the visible manifestation of the aging process in humans (senile canities). On the other hand, there is an early whitening of the hair probably linked to a genetic predisposition. Many hypotheses are put forward to explain this phenomenon. In particular, a decrease in the activity and expression of tyrosinase, a defect in the transfer of melanin from the melanosomes into keratinocytes for example.

 The change in hair color can also come from:. Nutritional, enzymatic (phenylketonuria) and vitamin deficits.

Medicines (chloroquine).

 Following chemotherapy and radiotherapy.

Diseases like vitiligo, progeria and Down's syndrome.

 The production of melanin at the level of the hair follicles takes place just above the dermal papilla and it is at this level that the transfer of melanin takes place towards the keratinocytes which will give birth to the hair shaft.

In the case of canities, these melanocytes disappear.

 At the level of the human hair follicle and more specifically in the external epithelial sheath, there are amelanotic melanocytes (which do not produce melanin) which have a significant proliferation capacity. They constitute a reservoir in the case of leukoderma (ex / vitiligo) and could migrate under certain conditions and repigment white hair.

 For the treatment of skin depigmentation linked to blockages of the transformation of tyrosine into melanin, such as for example vitiligo, application WO 92/20354 describes a composition containing, in a physiologically acceptable medium, a pseudocatalase.

 By pseudocatalase is meant a physiologically acceptable compound which catalyzes the disproportionation of H2O2 in vivo in a manner analogous to a catalase.

 This pseudocatalase is a coordination complex of Fe (II), Cu (I) or Mn (II), the ligand being bicarbonate.

 The article by K. Schallreuter (Pseudocatalase is a bis-manganese IIIEDTA- (HC03) 2 complex activated by UVB or natural sun; J Investing Dermator Symp Proc 1999 Sep; 451; 91-6) mentions the use of a

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mélange d'hyrogénocarbonate de sodium et de manganèse ayant une activité pseudocatalase pour le traitement du vitiligo.

mixture of sodium hyrogenocarbonate and manganese having a pseudocatalase activity for the treatment of vitiligo.

 The Applicant has found, quite surprisingly, that it is possible to treat canities by applying to the keratin fibers a composition containing in a physiologically acceptable medium a chemical catalytic system behaving like a pseudo-oxidase capable of mimicking the oxidase activity without the drawbacks associated with the use of an enzymatic system.

 The present invention therefore relates to a process for the treatment of canities which consists in applying to the hair a composition containing in a physiologically acceptable medium a chemical catalytic system mimicking the oxidase activity.

hydrogénocarbonates alcalino-terreux et leurs mélanges, les proportions du premier constituant et du second constituant étant telles que :

lavec [Mn (II) 0 IHCO31 lavec [Zn (n) 0 IHCO31 - < lavecMn (II)] Zn (II) 0 IHCO31

où [Mn (II)], [Zn (II)] et [HCO3] représentent respectivement les concentrations molaires en Mn (II), Zn (II) et HCO3 dans la composition. The method of the invention consists in applying to the keratin fibers a composition containing in a physiologically acceptable medium an effective amount of a catalytic system comprising a first constituent chosen from the salts and oxides of Mn (II) and / or Zn ( II) and their mixtures and a second constituent chosen from alkaline hydrogen carbonates, the

alkaline earth hydrogen carbonates and their mixtures, the proportions of the first constituent and of the second constituent being such that:

lavec [Mn (II) 0 IHCO31 lavec [Zn (n) 0 IHCO31 - <lavecMn (II)] Zn (II) 0 IHCO31

where [Mn (II)], [Zn (II)] and [HCO3] represent respectively the molar concentrations of Mn (II), Zn (II) and HCO3 in the composition.

Generally, the ratio "-'- 'varies from 10-5 to 10-1, preferably from [HCO3] 10-3 to 10-2 and is typically of the order of 5. 10-3.

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Dans le cas de Zn (II) seul, le rapport' est général d'un ordre de r/CL/g]

10 à 100 fois supérieur au rapport dans le cas de Mn (II) seul.

In the case of Zn (II) alone, the ratio 'is general of the order of r / CL / g]

10 to 100 times greater than the ratio in the case of Mn (II) alone.

Typically, this ratio is 10-4 or more, preferably 10-3 or more, and preferably on the order of 5. 10. 1.

généralement de 10' à 10'\ de préférence 10-3 à 10-2, ce rapport étant choisi plus élevé lorsque la proportion de Zn (II) dans le mélange s'accroît. In the case of a mixture of Mn (II) and Zn (II), the ratio varies

generally from 10 'to 10', preferably 10-3 to 10-2, this ratio being chosen higher when the proportion of Zn (II) in the mixture increases.

 Generally, the molar concentration of Mn (II), Zn (II) or Mn (II) + Zn (II) in the final composition varies from 10-3 to 10 mM / 1, preferably 10-2 to 1 mM /! .

 When only one or more Mn (II) salts or oxides are used, the molar concentration of Mn (II) in the final composition is typically from 10-3 to 10-1 mM / 1, preferably 10-2 to 10 -1 mM / l.

 Preferably, when the catalytic system comprises only one or more salts or oxides of Zn (II), the concentration of Zn (II) in the final composition is from 5.10-2 to 10 mM / l, better still from 5. 10-1 at 1 mM / l.

 Among the salts of Mn (II) and Zn (II) suitable for the present invention, mention may be made of chloride, fluoride, iodide, sulfate, phosphate, nitrate and perchlorate, salts of carboxylic acids and their mixtures.

l'iodure de Mn (II), le nitrate de Mn (II) trihydraté, le bromure de Mn (II) et le perchlorate de Mn (II) tétrahydraté, et le sulfate de Mn (II) mono hydraté. By way of example, there may be mentioned manganese chloride, manganese carbonate (for example rhodochrosite), Mn (II) difluoride, Mn (II) acetate tetrahydrate, Mn (II) lactate trihydrate , Mn (II) phosphate,

Mn (II) iodide, Mn (II) nitrate trihydrate, Mn (II) bromide and Mn (II) perchlorate tetrahydrate, and Mn (II) sulfate monohydrate.

Particularly preferred salts are MnCIs and ZnCIs.

 Salts of carboxylic acids also include salts of hydroxy carboxylic acids such as gluconate.

 Among the alkaline and alkaline earth hydrogen carbonates, mention may be made of the sodium hydrogen carbonates of Na, K, Mg, Ca and their mixtures, preferably sodium hydrogen carbonate.

 As indicated previously, the chemical catalytic system according to the invention constitutes a pseudo-oxidase in that it oxidizes polyphenols, in the presence of oxygen, as would a natural enzymatic catalyst having a polyphenoloxidase activity.

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On the other hand, the catalytic system according to the invention has no pseudocatalase activity in the sense that it does not cause the disproportionation of hydrogen peroxide to 0.3% by weight (ie 1 volume of oxygen).

 In addition, the pseudo-oxidase activity is linked to the use of the catalytic system according to the invention. Thus, each of the constituents of the catalytic system taken separately has no pseudo-oxidase activity. Just as the replacement of the salt of Mn (II) or Zn (II) by another salt, Fe, Cu or even Mn (III) does not lead to a catalytic system having a pseudooxidase activity.

 Without wishing to be bound by a theory, it is believed that the catalytic system according to the invention compensates for an insufficiency of the natural tyrosinase activity.

 The physiologically acceptable medium can be any medium which can be applied to the keratin fibers and which does not harm the catalytic effect of the catalytic system.

 Thus, the composition can be in the form of a liquid, a gel or a cream.

Among the media suitable for the formulation of the compositions according to the invention, mention may be made of water (in particular distilled or permuted) and water / alcohol mixtures.

The alcohols are preferably lower alkanols (Ci-Ce) such as ethanol and isopropanol and alkanediols such as ethylene glycol, propylene glycol and pentane diol.

The physiologically acceptable medium preferably comprises water (in particular distilled or permuted) or a water / alcohol mixture, in particular water / ethanol.

The amount of alcohol in the water / alcohol mixture can represent up to 80% by weight of the water / alcohol mixture, preferably 1 to 50% by weight and better still 5 to 20% by weight.

 The compositions according to the invention can also comprise any conventional adjuvant, in the usual proportion, which does not harm the desired properties.

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EXAMPLE: A treatment composition according to the invention was prepared by adding to a buffer solution of Dulbecco's NaHCO3 and MnCb in amounts required to obtain the following molar concentrations: NaHCO3 1 No MnClz: 1 mM / 1 A white hair was pulled out and placed this hair in a drop (5gel) of Dulbecco's pad placed on a glass slide. 5 l of the treatment composition were added to the drop (instant t0) and a photograph of the hair was taken. The hair was then photographed after 1 minute (time t 1) and 2 minutes (time t 2) in the treatment composition.

 Figure 1 is a reproduction of photographs of the hair at times tu, tri and t2.

 We see that the root of the hair (right part of the hair in the photographs) is clearly pigmented compared to the control (photograph of the hair at time to).

Claims (12)

 1. A method of treating canities, characterized in that it consists in applying to keratin fibers a composition comprising, in a physiologically acceptable medium, an effective amount of a catalytic system comprising a first constituent chosen from the salts and oxides of Mn (II) and / or Zn (II) and their mixtures and a second constituent chosen from alkaline hydrogencarbonates, alkaline earth hydrogencarbonates and their mixtures, the proportions of the first and second constituent being such that:

 washed [Mn (II) 0 [C <9J lavec [Zn (II) 0 [C6'J - <lavecMn (n)] Zn (IIO Lc j

 where [Mn (II)], [Zn (II)] and [HCO3] represent respectively the molar concentrations of Mn (II), Zn (II) and HCO3 in the composition.

2. Method according to claim 1, characterized in that the ratio "varies from 10-5 to 10 '\ preferably from 10-3 to 10-2 and better is of the order IHCO31 of 5. 10-3. 3. Method according to claim 1 or 2, characterized in that the ratio '-L- varies from 104 to <1, preferably from 10-3 to <1, and better of the order of HC03 5. 10-1 . 4. Method according to any one of the preceding claims, characterized in that the ratio [Mn -I - 'vane from 10-5 to 10, of varIe e a, e preferably 10-3 to 10-2. <Desc / Clms Page number 7>

5. Method according to any one of the preceding claims, characterized in that the molar concentration of Mn (II) and / or Zn (II) in the composition is from 10-3 to 10 mM / 1, preferably from 10- 2 to 10 mM / l 6. Method according to any one of claims 1 to 4, characterized in that the molar concentration of Mn (II) in the composition is from 10-3 to 10-1 mM / 1, preferably 10-2 to 10- 1 mM / l.  7. Method according to any one of claims 1 to 4, characterized in that the molar concentration of Zn (II) in the composition is 5. 10-2 to 10 mM / l, preferably 5. 10-1 to 1 mM / l.  8. Method according to any one of the preceding claims, characterized in that the salts of Mn (II) and of Zn (II) are chosen from chloride, fluoride, iodide, sulfate, phosphate, nitrate, perchlorate, the salts of carboxylic acids and their mixtures.  9. Method according to claim 8, characterized in that the salt of Mn (II) and / or Zn (II) is chloride.  10. Method according to claim 9, characterized in that the salts of carboxylic acids are salts of hydroxylated carboxylic acids.  11. Method according to claim 10, characterized in that the hydroxylated carboxylic acid salt is gluconate.  12. Method according to any one of the preceding claims, characterized in that the hydrogen carbonate is chosen from sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate and their mixtures.